Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
  • C09B45/24—Disazo or polyazo compounds
  • C09B45/26—Disazo or polyazo compounds containing chromium

Definitions

• the invention relates to metal complex dyes and their production and use, in particular for dyeing leather in dark brown to black shades.
• benzidine dyes are still used to dye leather in black shades, but these are not harmless from a toxicological point of view.
• the present invention was therefore based on the object of providing, above all, black leather dyes which are not benzidine derivatives and which have good hiding power and good fastness properties, in particular light and wet fastness properties.
• the dyes of formula (1) do not contain a fiber reactive group, i.e. no group that is able to react with cellulose or polyamide material to form a chemical bond under the usual dyeing conditions.
• the radical A bears in o-position to a hydroxy group Diazogru p pe.
• the residues A and B can also carry one or more further substituents, e.g. low molecular weight alkyl or alkoxy, chlorine, bromine, nitro, cyano, sulfo or acylamino.
• Low molecular weight alkyl or alkoxy groups are to be understood as meaning those with 1-6, preferably 1-2 carbon atoms and "acylamino" means low molecular weight alkanoylamino, alkylsulfonylamino and alkoxycarbonylamino residues as well as aroylamino and arylsulfonylamino residues.
• corresponding methoxy compounds or corresponding compounds whose hydroxyl group has been tosylated are also suitable, such as anisidine, 4- or 5-chloroanisidine, 4- or 5-nitroanisidine, anisidine-4- or -5-sulfonic acid, or tosylated 1-hydroxy-2-aminobenzene, the methoxy or 0-tosyl group being converted into an OH group during the metallization.
• Compounds with these groups are used especially when the corresponding 1-hydroxy-2-amino compounds couple poorly.
• A is preferably the residue of a 1-hydroxy-2-aminobenzene which is substituted by chlorine, nitro and / or sulfo.
• A represents the residue of a 1-hydroxy-2-amino-4-nitrobenzene, which optionally also carries a sulfo group.
• Preferred coupling components B are the following: phenol optionally substituted by low molecular weight alkyl or alkoxy, amino or acylamino, where acylamino has the meaning given above, resorcinol, m-phenylenediamine, optionally substituted in the 4-position by sulfo, chlorine, methyl or methoxy, naphthols which are optionally substituted with low molecular weight alkyl or alkoxy, chlorine, acylamino or sulfo, where acylamino has the same meaning as given above,
• 5-pyrazolones or 5-aminopyrazoles having in the 1-position a position-3 is optionally, possess with chlorine nitro low molecular weight alkyl or alkoxy or sulfo-substituted phenyl or naphthyl radical and a C l -C 4 alkyl group, particularly a methyl group ,
• Acetoacetic anilides and benzoylacetic anilides which may be substituted in the anilide core with chlorine, bromine, low molecular weight alkyl, alkoxy or sulfo groups, or 6-hydroxy-3-cyano- or 6-hydroxy-3-carbonamido-4-alkyl-2-pyridones, the 1-position by low molecular weight, optionally substituted alkyl, for example Methyl, ethyl, isopropyl, ⁇ -hydroxyethyl, ⁇ -aminoethyl or y-isopropoxypropyl or substituted by phenyl, and in the 4-position can carry a low molecular weight alkyl group, especially methyl.
• the coupling component B is a 1- or 2-naphthol, m-phenylenediamine, resorcinol, p-alkyl (C l -C 6) -phenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetanilide represents wherein the phenyl group in the latter two compounds can be substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro or sulfo.
• the known metallizable dyes are particularly suitable, for example those listed in the "Coulor Index" as mordant dyes.
• D is preferably the residue of a 1-hydroxy-2-aminobenzene or 1-amino-2-hydroxynaphthalene, which is also substituted by nitro and / or sulfo.
• K preferably represents the remainder of one of the following coupling components: 1-naphthol or 2-naphthol optionally substituted by sulfo and / or amino, phenol substituted in the p-position by C 1 -C 6 alkyl, optionally 1- or 2 substituted by sulfo -Naphthylamine, l-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, it being possible for the phenyl group in the latter two compounds to be substituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, chlorine or sulfo.
• Particularly preferred dyes according to the invention are the compounds which are in the form of the free acid of the formula (3) where A 'is the residue of a 1-hydroxoxy-2-aminobenzal which is substituted once or twice by chlorine, nitro or sulfo, B ' is a 2-naphthol, m-phenylenediamine, resorcinol, p-alkyl (C 1 -C 6 ) -phenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, where the phenyl group in the latter two compounds can be substituted by C -C alkyl, C 1 -C 4 alkoxy, chlorine or sulfo K '1-naphthol or 2-naphthol optionally substituted by sulfo and / or amino, phenol substituted in the p-position by C 1 -C 6 alkyl, optionally 2-naphthylamine substituted by sul
• the metallizable compounds of the formula (4) are obtained by methods known per se, for example by using an amine of the formula diazotized and with the coupling component of the formula couples at alkaline pH. The amino group is then diazotized on the naphthalene and coupled with a coupling component B.
• a and B have the meaning given above.
• the 1: 2 chromium complexes of the formula I given above which contain a dye of the formula (2) and a dye of the formula (4), are prepared, for example, by first reacting one of these dyes, preferably dye (2), with a chromium donating agent to give a 1: 1 complex. It is then converted into a 1: 2 complex by reaction with the other dye. This conversion is conveniently carried out in neutral to weakly alkaline medium, in an open or closed vessel, at an elevated temperature, e.g. at temperatures between 50 and 120 ° C.
• organic solvents e.g. Alcohols or ketones work or in aqueous solution, with additions of solvents such as e.g.
• a further process for the preparation of the 1: 2 chromium complexes of the formula I given above consists in firstly a 1: 2 chromium complex of the formula 7 produces, diazotized this in the usual way, for example with hydrochloric acid and sodium nitrite solution, and then couples it with a coupling component HB.
• D, K, A and B have the meaning given in formula (1).
• the new chromium complex dyes obtainable by the above processes are advantageously isolated in the form of their salts, in particular alkali metal salts, such as lithium, potassium, but above all sodium salts, or also ammonium salts. They are suitable for dyeing the various natural or synthetic polyamide materials, such as wool, silk, synthetic polyamide fibers, polyurethanes, but in particular for dyeing leather.
• the new dyes are strong in color and cover well. They have good drawability and good fastness properties such as washing, water, sweat, rubbing, diffusion, light, acid and alkali stability. Furthermore, they are largely insensitive to Ca salts in the dye bath, which is usually the case Permitted use of non-softened water.
• the good build-up ability on various types of leather deserves special mention, both on leather tanned only with chromium salts and on leather retanned with vegetable or synthetic tanning agents. You get strong brown to black shades.
• the mixture is heated to 80-85 ° and at the same time the pH of the suspension is increased to 7.5 to 8 by adding 5N sodium hydroxide solution and is kept at this temperature and constant pH by further adding 5N sodium hydroxide solution until the Starting products have disappeared.
• the new, chromium-containing dye is isolated by spray drying. It is a dark powder that dissolves in water and dyes leather in black shades of good fastness.
• the mixture is heated to 80-85 ° and kept at this temperature and pH of 7 by adding 5N sodium hydroxide solution until the starting products have disappeared.
• the new, chromium-containing dye is precipitated by adding sodium chloride. It is filtered off and dried. After drying, it is a dark powder that dissolves in water and dyes leather in black tones.
• the mixture is heated to 80-85 ° and kept at this temperature and pH of 7-7.5 by adding 5N sodium hydroxide solution until the starting products have disappeared.
• the new, chromium-containing dye is isolated by evaporating the suspension. After drying, it is a dark powder that colors leather in real brown tones.
• 30.9 parts of the monoazo dye from diazotized 4-nitro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene are stirred with 27.2 parts of chromium chloride hexahydrate in 800 parts by volume of ethylene glycol at 120-125 ° until the starting compound has disappeared.
• the mixture is heated to 80-85 ° and at the same time the pH of the suspension is increased 7-7.5 by adding 5n sodium hydroxide solution and holding it at this temperature and constant pH value by further adding 5n sodium hydroxide solution until the starting products have disappeared.
• the new chromium-containing dye obtained is precipitated by adding saturated sodium chloride solution, filtered off and dried. It is a dark powder that dissolves in water and dyes leather in black shades of good fastness.
• Dyes with similar properties are obtained if the 1: 1 chromium complex of the compound mentioned in column I is reacted in a ratio of 1: 1 with the disazo dye listed in column II.
• the dyes dye leather in the tones given in column III with good fastness properties.
• the black dyeings obtained in this way are distinguished by good fastness properties and good hiding power.

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Citations (4)

• 1981
  • 1981-03-23 EP EP19810810111 patent/EP0037377B1/fr not_active Expired
  • 1981-03-23 DE DE8181810111T patent/DE3165170D1/de not_active Expired

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